Role of Processing Aids in the Extrusion

of Molten Polymers#
E. C. ACHILLEOS', G. GEORGIOU', and S . G. HATZIKIRIAKOS2*
'Departmentof Mathematics and StQtistics
P.O. Box 20537
University of Cyprus
1678 Nicosia, Cyprus

2Department of Chemical Engineering

The University of British Columbia
221 6 Main Mall
Vancouuer,BC 6VT 124, Canadu
Froduct quality and, in general, processing windows and rates of production in the
extrusion of molten polymm are limited by various flow instabilities (mainly melt
fi-acture)that are observed at high production rates. While there still are unresolved
issues in comprehending these phenomena, industry demands for process optimization dictate the employment of processing aids (PAS)for product quality improvement and energy requirement reduction. In this review paper, most commercially
used processing aids (PAS)are discussed, namely, fluoroelastomers. stearates, small
amounts of polymers blended with the process polymer, and the newly discovered
boron nitxide as pure and in combination with other fluoroelastomers. This paper
focuses on the appropriate and optimum usage of the various PAS as well as on the
mechanism that underlies their action for flow enhancement and instability elimination. Finally, numerous experimental observations are discussed, and several
examples are illustrated.
1. ~YTIIODUCTION

t is well known that commercial polymer processing

operations, such as &er spinning, f
ilm blowing, profile extrusion, and various coating flows, &%it flow
instabilities, which manifest themselves as distortions
on the product surface. Consequently, these distortions
pose a limitation in the rate production that threatens
the economic feasibihity of the processes (1-8).These
phenomena of surface irregularities are collectively
known as s b h h / m e l t f m C t w e phenomena. other
typesof instabilities that may OCCUT in polymer processing at high rates of production, such as draw resonance and elastic instabilities, will not be examined in
the present review.
In extrusion processes, the extrudate distortions are
first observed when the volumetric flow rate, and, consequently, the shear stress, exceed a critical value. The
severity of the distortions (amplitude and irregulartyl
increases with increasing flow rate (3,9-12).Thus,

'Dafieated tothe lnemoryof Dr. Charles w.Stewart, an imnstlgator* made

8orrTBl CXCCPUOIld eonttibutblU3 the -Of
alds.
*AuthorrrsponsiMefor conrspdmce.emaIk h a t z i k J & h ~ . u b c . c a

the production rates of commercially acceptable products are limited to the ones below these critical values.
In order to overcome these difficuties and to render
the processes economically feasible, processing aids
(PAS) are frequently used. PAS eliminate flow instabilities or postpone them to higher flow rates. The end
result is an increase of the productivity as well as an
energy cost reduction, while high product quality is
maintained.
The purpose of this review is to examine traditional
and new pmcessing aids that have been investigated
over the past two decades and to discuss their performance in melt hcture elimination, so as to elucidate the role of these materials in instability elimination
and polymer processability improvement. The effect of
PAS on the rheologid properties and the instability
(melt fracture] elimination is also discussed.The factors that determine the additive performance, such as
concentration, dispersion quality. and interactionsbetween additives, additive and polymer, and additive and
die surface, are also examined. The various mechanisms by which Merent types of processing aids help
eliminate the instabilities are reviewed as well. Section
2 discusses the various melt fi-acture phenomena in

JOURNAL OF VINYL & ADDITIVE TECHIVOLOGY,MARCH 2002, Yo/.8, No. 1

E. C.Achilleos, G. Georgwy and S. G. Hatzikiriakos

general and their origin. Wall slip, which is normally
present, is also briefly discussed and its relation to melt
fi-acture is addressed. Section 3 reviews the traditional
processing aids such as stearates, fluoropolymers, lubricants and coatings of die materials. Polymer blending in general with concentrations of the minor component of the order of 0.1% and higher, as a means of
processing aid is also presented. Section 4 discusses
new processing aids, such as boron nitride powders,
as well as combinations of boron nitride with fluoroelastomers. These new PAS eliminate melt fi-acture and
enable polymer processing at shear rates that are significantly higher than those permitted by conventional
ones. In fact, they postpone the critical shear rates for
the onset of instability at rates within the gross melt
fi-acture regime, rates not accessible with conventional
PAS. The conclusions and general directions for future
investigations are summarized in Section 5.
2. THE NATURE AND ORIGINS OF POLYlUER
EXTRUSION INSTABILITIES
2.1. The Flow Curve

The flow instabilities that occur in extrusion processes can be better explained by looking at the different flow regimes of the apparent flow curve (3.4,11,
12).This is a logarithmic plot of the wall shear stress
versus the apparent wall shear rate when a capillary
rheometer is used, or the plot of the pressure drop

versus throughput rate when a processing equipment

is used. In the latter case, it is more strenuous to extract the fundamental quantities of shear stress due to
the large pressure associated with the entrance. Figwe 1 depicts a typical apparent flow curve of a h e a r
polyethylene melt, obtained using a capillary rheometer. The apparent shear rate, +A, is defined as (13):

. =32Q

y*

7rD3

where Q is the volumetric flow rate, and D is the diameter of the capillary. The wall shear stress, uw, is
defined as (13):
- A P - APITw

4L/D

where L is the length of the capillary, A P is the total

pressure drop driving the flow, and AP,, is the end
correction for the pressure drop. Figure 1 also represents typical behavior of a linear polymer in general.
Polymers such as LDPE and PP do not exhibit the
stick-slip flow regime as explained below. Four distinct
flow regimes can be identified in Rg. 1. Initially, the
flow is stable, and the shear stress increases "linearly"
(log-log plot) with apparent shear rate (power-law behavior), while the extrudate has a smooth and glossy
appearance. When the shear stress reaches a first critical value (crcl), small amplitude, periodic distortions

m. 1. Qpicclrjbw curuefor UnearpolyethyIene acbuded in apiston driven cqpillnry tllustmting the various regions of instability.
8

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY,MARCH 2002, Vd. 8, No. 1

Role of Processing Atds in Exbusion

appear on the exbudate surface. This instability is accompanied by a cllange in the slope of the flow curve,
as reported by many investigators (3.4,14-16).This
instability is observed up to the end point of the left
branch of the flow curve (often referred to as the low
flow rate branch) and is genereferred to as sharkskin or surface m e l t w e . A second instability occurs when the shear stress exceeds a second critical
value (crc2) and only within a certain range of apparent
flow rate values. It corresponds to the region separating the two branches of the flow curve, and is usually
referred to as stick-slipinstability or spurt phenomenon
or oscillating melt fracture. In this regime, the flow
ceases to be stable when a controlled rate capillary
rheometer is used. Instead, pressure, and thus shear
stress, oscillates between two extreme values and alternate distorted and smooth zones appear on the extrudate surface (3,4,9, 11, 12,17-19).Finally, at even
higher apparent shear rate values, the flow becomes
again stable, whereas the extrudate exhibits gross, irregular and chaotic distortions. This type of instability,
is referred to as gross meltfracture, and corresponds to
the right branch of the flow curve (1,3,4,11,12,
20,
21,22).
Thorough reviews on extrusion instabilities have
been published, and the mechanisms responsi%le for
these instabilities have been the subject of ongoing
debate (1,5,6,7.23. 24).Various polymer rheologid
properties, such as wall slip, melt compressibility,melt
viscoelasticity, non-monotonic shear stress-shear rate
law, viscous heating;, viscoelastic rupture, and local
stick-slip, which may be simultaneously involved, can
be held accountable (5,6,7,24. 25,26).One has to
distinguish between the mechanisms responsible for
each type of instability. For the case of sharkskin melt
fracture, there is general agreement about its location
of occurrence. It takes place at the exit of the die, either
because of rupture. as the boundary condition changes
from no-slip or partial slip to a shear-free one, which
results in a highly extensional flow (14,27,28,291,or
because of local stick-slip at the exit as a result of
polymer molecule disentanglement (30).On the other
hand, gross melt fr-acture occurs at the entrance of the
die because of the abrupt contraction (20,31).Since
this review focuses on the elimination and not on the
mechanisms that cause these instabilities, the latter
will not be discussed fiather.
2.2.

wdl slip

Wall slip usually accompanies the instability phenomena under discussion. It is, indeed, the phenomenon most thoroughly studied in the literature, both

experimentallyand computationally.
Sharkskh instability has been attributed by many
researchers b small d q m l w t s from the no-slipboundary condition, which am be accompanied by a sharp
change in the flow curve slope (3.4.11, 32.33).Some
experiments have indicated that sharkskin or surface
melt fi-acture is suppmsed byni
the adhesion
between the fluid and the wall (3,s).
whereas others

have shown that slip promotion suppresses the instability (28,35,36). Slip velocity increases when certain
additives are used and as a result shear stress is reduced, shifting the flow curve to higher shear rates
(37,381.
This is because both the slip velocity and the
critical shear stress for slip are strong functions of
the work of adhesion between polymer and interface
(37-40).It is the shear stress reduction, rather than
the slip velocity increase, that suppresses the instability at a particular flow rate, when additives are used.
Moreover, it is also the type of slip that causes sharkskin to occur. over clean swfaces, polymer slips locally
by a stick-slip mechanism that creates the well-known
schallamach waves similar to those in the sliding of
elastomers over metallic surfaces (41).Polymeric fluids
are not much Merent from elastomers at high enough
shear rates, since their elastic properties prevail in
short time scales.
At low shear rates, slip was speculated to be caused
by an adhesive failure, that is, stress-induced strain
detachment of polymer molecules form the wall (3.4,
1 1, 42,43).Experiments have shown that there is a
strong correlation between the work of adhesion of the
polymer/wall interface and the onset of slip (39,40)
and this finding implies adhesive failure. As discussed
above, experiments have indicated that the sharkskin
originates at the die exit region because of polymer
rupture, as a result of the high stresses that develop
around the die exit (14,27,44, 45).This mechanism
is certainly consistent with the violation of the no-slip
boundary condition. Gross melt fracture originates
near the die entry region, where unstable vortices appear and symmetry is lost (35,44, 4.6,47). Cohesive
Mure, that is sudden chain disentanglementand rupture of chains near the wall. can account for slip in
the gross melt fracture regime, and thus for the unstable and v i r t d l y plug-flow behavior (20,48). Overall, the experiments in the literature indicate the presence of weak slip (small deviations from the no-slip
conditions) in the sharkskin regime, which is attributed to adhesive failure and of strong slip in the grw
melt fi-acture regimes, which can be explained by cohesive failm.
Other experiments have shown that slip is not at all
present in the sharkskin regime, indicating that other
phenomena also contribute to this instability (30,35,
49,50).The stick-slip and the gross melt fracture instabilities have been modeled by many researchers
using a combination of a slip law with the small but
finite compressibility of polymers (51-56)or with a
viscoelastic model (57-60).Both compressibility and
viscoelasticity can account for the storage of elastic
energy that sustains the pressure and flow rate oscillations in the stick-slip regime. Melt compressibility in
the reservo&was shown to be a necessary (9)but not
sufficient condition (61)for the variations in the pressure and flow rates in the stick-slip regime. Cohesive
Mure at high shear mtes was attributed to hardening
of the polymer, which undergoes a relaxation transition from a fluid to a highly elastic solid-like state (47,

JOURNAL OF VINYL & ADllITlVE TECHNOLOGY,MARCH m 2 , Vol, 8, No. 1

E. C. AchiUeos, G. Georgwu, and S . G. Hatzikiriakos

62-66). Elucidation of the phenomena that cause flow
instabilities is important in understanding the m e r ent mechanisms by which the processing aids lead to
their elimination.
Processing aids used for instability elimination include additives and surface coatings. Most of these
additives or modifications target at slip promotion
that leads to lower stresses and pressures. Additives
used as dispersions at low concentrations in the base
polymers act as lubi-icants. They increase slip through
reduction of the apparent viscosity, and as a result
the pressure required for the extrusion process is reduced, thus shifting the instabilities to higher flow
rates (67-69). Surface coatings also act as lubricants
and modify the melt-wall interfacial interactions, decreasing the pressure. and consequently the shear
stress required for a specific flow rate (30, 70). They
thus prevent the rupture of the polymer as it exits the
die. Many industrial patents have been issued for the
incorporation of various processing aids in extrusion
processes (71-73), which justifies the ongoing intense
academic and industrial research contacted in this
area.

3.TRADITIONALPROCESSING AIDS
3.1 Flaomymers

Fluoropolymem have been traditionally used as processing aids in the extrusion of commercially important
polymers, including linear low-density polyethylene
(LLDPE), high-density polyethylene (HDPE), polypropylene (PP), copolymers of ethylene, propylene and
hmdiene (EDPM), and others. Low concentrations of
fluomelastomers (down to 500 ppm) in dispersion with
the processing polymer can significantly enhance product quality and processability, not only by eliminating surface defects, but also by reducing torque and
power requirements as well as die plate pressure (67,
68).Fluoroelastomers used as PAS include Dyneon's
DYNAMAR@,
DuPont's m N @ (a copolymer of vjnylidene fluoride, hexaethylene and/or tetrafluoroethylene). W o n t ' s TEFLON@,and DFL (dry film type).
An important effect that fluoropolymers have, when
used in dispersion with the processing polymers. is the
increase of slip velocity, which is accompanied with a
reduction of pressure. Thus, the apparent shear stress
needed to extrude the polymer at a particular flow
rate is much lower, or alternatively, an increase in the
throughput rate is obtained at a given pressure drop
(67, 68,70, 74). This is accompanied by a delay of the
sharkskin instability to higher shear stresses. Athey
et at (68)
found that when a version of ~
N (vinyli@
dene fluoride, hduoropropylene 60:40)was used in
dispersion with HDPE, LLDPE, and PP. the shear stress
was reduced and the flow curve was smed so that
the sharkskin instability was postponed to higher
shear rates. The reduction of shear stress took place
up to shear rates of 1000 s-l, therefore eliminating
only the sharkskin and the stick-slip instability but
not the gross melt fracture. Similar results were found
10

when using a DYNAMAR@

brand additive (PPA-2231)
in extrusion of HDPE and LLDPE (67). Comparing
DYNAMAR? and TEFLON@,Wang (30)concluded that
while both induce slip and reduce stresses in the extrusion of HDPE and eliminate the sharkskin instability, TEFLON@is more effective in coating the die
surface, and, in addition, in eliminating the stick-slip
instability. Similar conclusions were reached by Hatzikiriakos et at (70).The shift of the flow curve and instability onset to higher flow rates is depicted in Fug. 2
typically for an HDPE. The wall shear stress is plotted
as a function of the apparent shear rate at a temperature of 180C. The data obtained by using an Instron
capillary rheometer and several dies of various lengths
and diameters to apply all required corrections (17).
As a result of the slippage, the shear stress at a given
apparent shear rate is reduced. Consequently, the
power/torque requirements for a given production
rate are reduced, and the production efficiencies are
increased (67, 68). This can be seen from Fig. 2,
where distortions in the presence of PA are only obtained at the point indicated as the onset of gross melt
fracture. That is the point where the two flow curves
merge. Therefore, the benefit from using a PA is that
for a given power requirement the production rate is
increased, while the product maintains its high quality, since the additives suppress the instabilities. As
discussed below, it was concluded fkom experiments,
that the additives migrate to the surface of the die,
creating a thin surface of coating and acting as lubricants. Recently, Migler et aL (75, 76) used optical
microscopy to prove this mechanism of migration and
die coating convincingly.
The phenomenon of PA particle migration to the wall
is also supported by the fact that fluoropolymer coatings of the die wall also lead to slip enhancement and
shear stress reduction. HatAkirkh s et at (37) used
W N @ and TEFLON@ PA to coat the surface of the
plates in a sliding plate rheometer. They found that
the coatings resulted in a significant decrease of the
critical shear stress for the onset of wall slip and in an
increase of the slip velocity. The critical shear stress
for the onset of slip, which is 0.1 MF'a for the clean
plate, could be as low as 0.027 Mpa with a TEFLON"
and 0.043 Mpa with W N @ coating. The shear stress
reduction ranged from 20 to 50%, depending on the
extrusion rate. TEFLON@ also increased the slip velocity and reduced the required shear stress for the flow
of PP in sliding-plate and capillary experiments (77).
TEFLON@was found to suppress the extrudate distortions of various LLDPEs up to about 1500 s-l (70).The
effect of the TEFLON@coating on the flow m e was
similar to the one depicted on Rg. 2. Tko other additives, DYNAMAR@
and DFL coated on capillary rheometer dies for the extrusion of HDPE. also resulted in
instability suppression for shear rates up to 1000 s-l
(34).Howe~er,it w a found
~
that while DYNAMAR@
promoted slip and reduced shear stress, DFL promoted
adhesion, and had no effect on the flow curve (34).
Experiments by Xing and Schreiber (78)also indicate

JOURNAL OF VINYL &ADDITIVE TECHNOLOGY,MARCH 2oM, Vol. 8, No. 1

Role of Processing Aids in Extrusion

HDPE (loo0 ppm of PA)

T=l80 "C

FYg. 2. Themw cunc of a D P E

evtruded in a pressure-dnven
. capillary rheorneter as &gin and in

the presence of afluoroelasbmer.

onsetof
SharkskinMF

onsetof
GrossMF

0.01
1

I0

100

lo00

loo00 lo0000

Apparent shear rate, s-l

that when dies are coated with either DYNAMAR@or

WP',via extrusiori of the fluoropolymm prior to the

processing polymer, slippage is enhanced and shear
stress is reduced.
When an additive is present either dispersed in the
polymer or as a coating, proper die conditioning is
needed prior to any equilibrium measurements. KazatcNrov et aL (77) found that when PP was extruded
through TFCFLON@-coatedcapillary dies, the shear
stress was reduced more with each subsequent run
(Rg.3),indicating that the fluoropolymer coating was
initially imperfect and after a long induction time it
was smoothed out, providing better lubrication and
larger reduction in the extrusion pressure. This phenomenon is even more pronounced when the additives
are used in dispersion. As the polymer is extruded,
the fluompolymer molecules accumulate on the die wall
causing a pressure/shear stress reduction. As the extrusion proceeds with time, the pressure is reduced
until equilibrium is reatched, and complete ellmination
of the sharkskin takes place (68.74). As the additive
level increases, the pressure reduction is higher, and
the time needed to equilibrium is shorter (74).
Increasing the additive level typically results in
geater pressure reduction, higher shear rates, and
thus higher production efficiencies (67, 74). while the
extrusion pressure and shear stresses are reduced
as a result of lubrication, an excessive amount of lubricant should be avoided, because it might lead to
lubrication of the extruder barrel, which can have undesired &&As (67).
In addition to the additive level, other factors that
critically &ect the additive performance and need to

be optimized. include the dispersion quality. the particle size, and the interactions with other additives
present in the processing polymer. Generally. the dispersion quality improves when the additive has a small
particle size 6.e. 5 pm) and a homogeneous dispersion
is prepared with intensive mixing. A two-step procedure
in which a master batch is first prepared and pelletized,
and then mixed with the process polymer is an effective route for preparjng homogeneous dispersions (67,
74). h the case of W N @ . diluting the fluomelastomer
in acetone prior to mixing was found to be beneficial
(79). The interactions with other additives that might
be present need to be minimized if not eliminated completely (74, 80,81. 82). Wester et aL (74) found that
the presence of anti-block agents slow the conditioning
curve (time needed for steady state) and that higher
additive concentration is required in order to have the
same conditioning curve as in the case of no additive.
It is generally agreed that fluoropolymm when used
in dispersion migrate to the wall of the die and create
thin coatings (68, 74, 75. 76, 79). Generally, fluoropolymers are more polar than the process polymers so
they migrate more easily to the wall. They are deformable at the extrusion temperatures so they can easily
form a coating on the die wall (68).
The m t i o n of secondary flows as a result of sharp entrance effects,
which create eddies, can assistparticle migration to the
wall (79). As in the case of coated dies, the interfacial
conditions determine the molecular mechanisms that
can either promote or suppress slip,with subsequent
results on the shear rate reduction and/or instability
suppression. Experiments show that with the exception
of DFL (34)fluompolymers act as lubricants, promoting

JOURNAL OF VINYL & ADL)ITWE ECHNOLOGV, MARCH 2oM, YO/. 8, NO. 1

11

E. C.Achilleos, G. Georgiou, and S. G. Hatzikiriak 0s

F?g. 3. ?he eff& of

a Temn@coating on the shear stress in the continuous extrusion Of POlyprOPYlene

mtsl.

slip. Slip promotion is attributed to the incompatibility of the host polymer with the fluoropolymer layer
(38,68,78).The experiments of Hatzikiriakos and
co-workers have shown that when fluoropolymers are
employed as PAS, the slip velocity increase is accompanied with a decrease of the critical stress for the onset of slip (34,37,38,70,77).
In addition, Anastasiades and Hap ** ' * ' (40)
a sessile drop method to measure the work of adhesion
between HDPE/LLDPE and clean as well as FE-coated
stainless steel. They found that VITOP and, more
profoundly, TEFLON@ reduce the work of adhesion between polyethylene and the surface. These findings
support the hypothesis that slip is a result of adhesive
failure, and that slip velocity and critical shear stress
for the onset of slip depend on the work of adhesion.
Slip models taking these phenomena into accounf have
been developed by Hatzikiriakos (38).Hill et d (39)and
Stewart (43).The fact that instability enhancement is
associated with the onset of slip for virgin resins is
somewhat inconsistent with the instability suppression effect that fluoropolymers have when they act as
lubricants. H
a
m and Dealy (34).hawever, point
out that the presence of either an adhesion or slip promoter can alter the variation of slip along the die, and
reduce the extensional strain upstream the die exit,
which according to Kurtz (14)is a determining factor
for the stresses that develop at the die exit and thus
for the occurrence of the instability.
12

c q i k r y expen-

To summarize this section, fluomelastomers such as

DYNAMAR@,TEFLON@,WON@,can be effective processing aids in extrusion processes, eliminating sharkskin and stick-slip instabilities, and providing a wider
range of production at lower cost. Optimization of the
additive performance requires knowledge of the effect
of the merent process parameters on the extrusion
process as well as understanding of the instability
suppressing mechanism involved. Fluoropolymers can
be used as additives to the resins (dispersed at sizes
less than 5 pm, by means of preparing a master batch)
or as coating agents to the die walls. They work properly at clean surfaces and optimum concentrations
(500-1000ppm), and exhiiit induction times before a
full effect is observed.
3.2 Stmrates
Stearates, such as calcium and zinc stearates, are
present in several commercial resins of both linear and
long-chain branched polyethylenes (83).
While there is
no experimental indication that stearates act as processing aids for linear low-density polyethylenes, there
is strong evidence that they promote slip and aid in
the reduction of instabilities in the case of metallocene
low-density polyethylene copolymers with long chain
branching (83).In typical transient capillary extrusion
experiments of linear low-density polyethylenes, the
load rises hitially with time until it reaches a steady
state. However, in the case of metallocene polyolefins

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY,MARCH 2#2, Vd. 8, No. 1

Role of Processing Aids in Exbusion

that contain steruates, the die-conditioningphenomenon is observed, :similar to the one depicted in Rg. 3.
In several experimental runs, HatzWriak0s et al. (83)
showed that in capillary experiments with metallocene
long chainbranched LLDPEs that contain stearates. the
pressure initially iises and then starts dropping. After
s e v d consecutive capillary extrusions, i.e.. by reloading the reservoir of the rheometer, pressure attained
its steady state value, indicating that complete conditioning of the die surface has been achieved. Comparison of Merent resins has shown that the conditioning is longer as t h e amount of long chain branching is
increased. The critical shear stress for the onset of slip
for these resins was 0.05 MPa, significantly lower than
the one corresponclhg to linear low-density PE resins
(0.1 MPa). Furthermore. sharkskin and stick-slip instabilities were observed only in the transient experiments, whereas in steady state, only gross melt fi-acture is observed. Gross melt fracture, accompanied
with a change in the slope of the flow curve, was observed at 0.33 Mpa, which is similar to the shear stress
values observed for polymer having conventional PAs.
Overall, the processing behavior of metallocene polyoleflns was similar l o that of polyethylene when fluoropolymers are used. Since no other additive was detected in the metallocene resins, it was concluded that
calcium stearate, wfuch are present in concentrations
of about lo00 ppm, iTCt as processing aid with a mechanism similar to that discussed for fluoropolymers.The
fact that stearates do not, to our howledge, enhance
the processability of linear low-density polyethylenes
could possibly be explained by investigating possible
interactions between stearates and LDPE as well as
with metallocene potyoleflns having a small degree of
long chainbranching. More experimental evidence and
systematic studies far resins with various concentrations of stearates are needed for more conclusions to
be drawn.

s.3 other Pdymer I

h d s
Hydromrbonsblended with the process polymer can
also act as PAs. This 1:echnique might involve not only
dispersing a s d quantity of PA into a process polymer, but also polymer blending to ratios of the same
order of magnitude. Although the notion of a processing aid has a meaning at small concentrations (typically less than 1%)).blending at higher concentrations
might also improve processing. Examples from the lite r & . ~ are
~ included hiere.
Blending of polypropylene (PP) with polytethyl vinyl
acetate) (EVA) for flow instability reduction of PP was
examined by Montoya et aL (84)with capillary rheometer experiments. They tested blends of concentrations
ranging h m O?! to 180% and found that the critical
shear rate for the onsel of fi-acture increased with EVA
concentration. Mechanical property measurements
have shown that while pure EVA has completely elastomeric behavior, blends of 50%PP and higher exhibit
thermoplastic behavior with yield stress that increases
with PP content. It was thus concluded that 15/6-20%o

EVA-PP blends provided good balance between the

mechanical properties and melt fracture behavior.
Fujiyama and Kawasaki (85)studied the capillary
flow properties of blends composed with various ratios
of PP and HDPE with low (L), medium 0and high (HI
melt flow index (MFI).They found that the flow curves
of the different blends (PPM/PEH. PPM/PEM. PPM/
PEL, PPH/PEM, PPL/PEM) were located between the
flow curves of the two virgin components. In the blends
in which PP had a lower or equal MFI with the PE, the
slope of the curves increased with decreasing PP content. The critical shear rate and the critical shear
stresses for the onset of melt fracture of the blends
were close to the ones determined by logarithmic additivity of the values that correspond to individual
component.
Blending of two incompatible polymers, a fluoropolymer (VITON@)and EDPM, in various proportions,
in order to improve the performance of one or the other
polymer, was experimentally examined by Shih (86,
87). Addition of a small amount of vrrON@(down to
0.4%) in EDPM, significantly reduced the shear stress
and improved the appearance of the extrudate. EDPM
improved the processing of vrrON@in a similar fashion. This effect was more pronounced as the vrrON@
concentration increased up to concentrations of 5%;
no improvement was observed with further increase of
VlTON@ concentration. It was experimentally determined that, during the extrusion of blends, the polymer used in small concentration created a build-up
layer on the die wall, indicatfng that a phase separation had occurred, in which the polymer used as additive accumulated on the wall.
The geometry of the die can also affect the additive
performance. Kanu and Shaw (79)found that dies with
180"entrance angles promote the migration of vrrON@
particles to the wall during EDPM extrusion. Reduction
of the capillary diameter in extrusion of EDPM, with
vrrON@ as a PA, resulted in a SNft of the flow curve to
higher flow rates (86,87). This indicates that longer
dies also promote particle migration. Detailed studies
of the sharkskin instability in various diameter dies
showed that when no additive is used, the critical
stress for the onset of instability for LDPE extrusion is
the same, but the amplitude of sharkskin increases
with increasing diameter (29).
Rosenbaum et aL (88)studied the use of PE as a
processing aid in the extrusion of FEP (tetra-fluoroethylene-polypropylene)resins.Capillary extrusion experiments of D P E (GRSN/7047) dispersed in small
quantity (0.1Yo) in FEP 4100, indicated that PE is an
efficient PA for eliminating melt fracture and stick-slip
instab%lity in the extrusion of fluoropolymers (Q. 4).
As a result of PE addition, the apparent flow curve is
shifted to lower shear stresses allowing for smooth
extrudates up to 1000 s-l. It is suggested that PE
particles, which have a lower viscosity than FEP, migrate to the wall. Furthermore, the atltlnity of PE for
metal surfaces, which is higher than the afbiiy of FEP
for metal, results in the coating of the surface by PE.

JOURNAL OF WNYL & ADlmVE TECHNOLOGY,MARCH 2002, Yo/. 8, No. 1

13

E. C.Achilleos, G. Georgiou and S. G. Hatzikiriakos

I

, # I ,

T=350C U D 4 0 D=0.762 mm

$3

cr

0.2

.E
c

-h

0.1 -

Q)

Fig. 4. 7 k EJkt of a small amount

of PE {GRSN-7047)on theflow
curue of an FJP resin at 350C.

0.08

v v

=I

0.06

fn

x 0.04
2
(P

(I)

ll A v

I10 V

0.02

V
V

A Teflon FEP 4100

v Teflon FEP 4100 + 0.1% PE

102

103

104

Apparent shear rate (&), s1

Furthermore, the low friction coefficient at the FEP-PE
interface results in the slip of the extruded FEP over
the thin PE-layer. Consequent&. this results in shear
stress reduction and in instability supression. The wall
coating mechanism is illustrated in Rg. 5. This will be
discussed in detail in the next section. However, it is
sufficient to say here that when a FEP/PE blend is
extruded through a clean die, the die-wall coating process starts during extrusion, requiring several runs for
reaching steady state. Under constant shear rate, the
shear stress goes through a maximum and levels off
when the coating is complete (Fig. 6). During this
process, particles of FEP are displaced by PE particles. Owing to the higher affinity of PE with the metal
wall, the PE particles, upon reaching the wall, cannot
be displaced by FEP ones. The time required to obtain
steady-state response was found to depend on the
process and geometry parameters. The time for achieving steady state decreased with increasing apparent
shear rate, and with decreasing diameter or L/D ratio.
These findings are consistent with the above mechanism. The latter suggests that the time for achieving
steady state is proportional to the time for complete
surface coating. A decrease in the diameter or the L/D
ratio reduces the area to be coated, and an increase in
the apparent shear rate increases the rate of the coating process. In both cases, the time required for complete coating and steady-state operation is reduced.
3.4 M e c h a n b m of aricpraticW and Die Chating

It is perhaps surprising that polyethylene can be used

as a processing aid in FEP extrusion for the reduction
14

of the extrusion pressure and the elimination of sharkskin in a similar fashion as fluompolymersare used in
PE extrusion. It is noted that fluoropoymers, such as
TEFLON@and FEP, have been used effectively as PAs
in the extrusion of PEs (15,30, 34, 67,68,70,89).As
discussed above, it is expected that PE would tend to
migrate towards the die wall during extrusion, since
its viscosity is lower than that of the FEP. In fact, it is
not the viscosity but the work of adhesion that allows
this process (migrationand wall coating)to take place.
It is the energy required to remove the polymer from
the metal surface that determines which component
eventually coats the die wall. Polyethylene has greater
adhesion to metal surfaces than FEP resins, so it is
not surprising that during extrusion experiments the
metal die surface eventually becomes coated with a
very thin layer of polyethylene. Since there is very little
adhesion between FEP and polyethylene at sufficiently
high shear stress, it appears that FEP slips over the
thin polyethylene coating on the die wall.
This, then, raises the question as to why a very
small quantity of FEP resin, when h e l y dispersed in
polyethylene, will completely coat the die wall during
extrusion. The answer again lies in the relative values
of the work of adhesion. Although the work of adhesion of FEP to metal is less than the work of adhesion
of polyethylene to metal, the work of adhesion of polyethylene to FEP is much less than either of these.Thus,
if a very small FEP particle dispersed in polyethylene
comes into contact with the metal die surface during
extrusion, there will be very little force at the FEP/polyI
ethylene interface acting to pull the particle off the

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 2002, Vol. 8, No. 1

Role of Processing Aids in Extrusion

Fig. 5. Wall coating mechanism to illustrate the action of Pas in extrusionprocesses.

0.20
T=325OC yA=104.2s-l
UD=40 D=.762 m m

2
z

0.16
a. Teflon FEP 4100
b. Teflon FEP 4100+0.1% PE

2
v

u)
u)

6. ?fan~ientCapiuc~y&swrx the eB& of the atMition of

0.1% of polyethylene on the transient response in the capillary
extrusion of FEP 4100 c l t 325"C,
iA= 104.2 S1,L / D = 4G and D =
0.762 m m
Rgj.

0.12

er

u)

tiia,

u)

0.08

er

(P

0.04

It
0

50 0

l a , , , , , II,,
50

,, ,

100 150 200 250

300

350

Time (t), min

JOURML OF VINYL & ADLHnVE TECHNOLOGY, MARCH 2oM, Vol. 8, No. 1

15

E. C.Achilleos, G. Georgwu, and S. G. Hatzikiriakos

surface. The polyethylene will slip over this interface

and will cause the particle to spread. On the other
hand, the force acting to pull the polyethylene off the
surface is the result of the wall shear stress during
extrusion. The o v e d result is that the FEP particles
accumulate, spread and eventually form a very thin
coating on the die over which the polyethylene can
slip.
Examination of a broad range of fluorocarbon/hydrocarbon blends has led to the foliowing general observations: To be effective, the minor component must
be in a finely divided state of particle diameter less
than about 0.2 pm and must be at a very low concentration of less than about 1% by weight. For optimum
performance, the viscosities of the two polymers should
be approximately equal. The relative work of adhesion
between the two polymers and the metal surface and
between the polymers themselves determines the final
performance. For example, fluoropolymers will displace nonpolar hydrocarbons with low work of adhesion, but will not displace polar polymers such as
nylon, polyesters or poly(methy1 methacrylate) from
metal surfaces because of the very high value for the
work of adhesion of these polymers to metals. For such
polymers it is difficult to identify a suitable processing
aid that would work in the same fashion.
4. BORON NITRIDE A NEW PROCESSING AID

The influence of a new processing aid, namely boron

nitride (BN), used either as an additive in dispersion
or in combination with other processing aids, is examined in this section. BN is a solid, inorganic compound, with a structure resembling thst of graphite. It
is thermally stable and chemically inert, and it is used
in combination with a blowing agent as a foam nucleating agent in commercial processing applications of
fluoropolymers. Boron nitride was used without a blowing agent in extrusion experiments, in order to examine its ability to improve processing of polyolehs and
fluoropolymers. This additive was found to increase,
by orders of magnitude, the maximum shear rates at
which the extrudate distortions appear, eliminating
completely sharkskin and the stick-slip instability,
while delaying signiacantly the gross melt fracture instability. It is noted that no other additive has been
reported to be able to delay gross melt fracture.
4.1 Boron N M d e Used as Pare Additive

The use of several BN powders as processing additives in extrusion of metallocene linear low-density
polyethylene (m-LLDPE) and TEFLON@ FEP/PFA resins was experimentally investigated employing capillary rheometers, with either annular or cross-head
dies, and larger-scale extrusion equipment (90-95).
The effectiveness of the additive was found to depend
on the die geometry, the temperature, the dispersion
quality, and the BN concentration and type.
Capillary rheometer e x p e ~ e n t shave indicated that
BN has a strong impact as a processing additive when
16

a cross-head die is used, whereas it has a small effect

when a circular die is employed (31,90,91. 93).In
these experiments, an Instron piston-driven capillary
unit, with various annular dies (D = 0.762 mm & L/D
= 0-40, D = 0.254 mm & L/D = 40). was employed
for extrusion of m-LLDPE (Exact 3128 and Exceed 166,
Exxon) containing 0.05?4o-O.l0hBN powder (CTF5)at
163C.For all geometries the virgin m-LLDPE resin
exhiiited the sharkskin instability around 40 s-l.Conversely, the sharkskin instability was eliminated when
BN was added and the flow became unstable at high
shear rates (200-250s-l).The flow curves of the virgin and the BN 61led m - W P E resins obtained using
a capillary rheometer with a die having D = 0.762mm
and L / D = 40 at 200 s-l are depicted in Flg. 7.Even
though the addition of BN powder eliminates extrudate distortions in the sharkskin regime, improving the
appearance of the extrudate, it has almost no effect on
the flow curve. In these experiments, BN completely
eliminated the sharkskin instability for the m-LLDPE
resin, but suppressed neither the stick-slip nor the
gross melt fracture instability.
Employment of a Nokia Maillefer moss-head die, typically used for wire coating applications, having similar
configuration with dies used in various processes, resulted in a significant enhancement of the additive
performance. Figure 8 illustrates the geometry of such
a die. Addition of BN powder (CTF5 type)to m-LLDPE
resin increased the maximal shear rate at which extrudates were smooth h m 40 s-l (correspondingto the
virgin resin) to up to 920 s-l,which is well above the
onset of the gross melt fracture instability (500s-l)for
the virgin resin (31,90-95).
On the other hand, addition of a small amount of BN (100-lo00ppm) changes
very little the flow curve of the polymer. This is illustrated in Fig. 9 for a linear low-density polyethylene
(Exact 3128).It can be seen that the flow curve remains
the same for all practical purposes, while the melt
fracture behavior changes spectacularly. Figure 10 depicts extrudate photos of sharkskin (Ffs.1Oa)and gross
melt fracture (Flg. lob) obtained with the virgin resin
and smooth extrudate (Fig.1Oc) obtained in the presence of BN well within the gross melt fracture regime,
i.e., conditions similar to those that correspond to Flg.
1Ob.
At a given temperature, the performance of the additive depends on its concentration at 163OC,the maximal shear rates for smooth extrudate were obtained
at low concentrations (0.02%BN), as can be seen in
Flg. 11 (31,90-95).It can be seen that at conditions
well within the gross melt fracture regime, the distortions disappear only at low BN concentrations (500
and 1OOO ppm),whereas for relatively high concentrations of BN (so00 ppm), these cannot be eliminated.
The effect of the temperature on the critical BN concentration was also studied using an Entwisle extruder
(90.91).
At 163C.the maximum allowable shear rates
were slightly higher than those obtained with the rheometer, but their concentration dependence was the
same, that is, the low additive concentrations had the

JOURNAL OF VINYL & ADDITIVE TECHNOLOGV,MARCH 2002, Vol. 8, No. 1

Role of Processing Aids in Exbusion

I

Hg. 7. Flow curves .for PE Exact

3128 with and without BN powder. Capiliary rheonteter experiments at 163C with D = 0.762
mm and L / D = 40.

#I

I ) I ,

smooth

a
Q

PE Exact 3128

5
0.1

T=163 OC,UD=40, D=0.762 mm

-a
I

best effect on instakiility elimination. However, when

the temperature was raised to 204C. increasing the
concentration improved the performance of the additive. The optimum caacentration for BN to 204C was
found to be 0.5%. Tkus might be attributed to a temperature dependent txitical dispersion concentration,
above which the BN F&cles agglomerate.
When BN was employed with TEFLON@fluoro-copolymers of tetrafluoroethylene/hexafluoropropylene
FEP 100/3100/4100/5100),the maximum allowable
shear rates using the c=xtruderwere significantly higher
than using the capillary rheometer, possibly because

m.8. Cro~s-headdief

, 1 1 1 1

virgin resin

0.05% BN
,,I

of better mixing of the additive with the polymer in

the extrusion barrel (90.91). Again, the presence of
BN increased the maximum allowable shear rates to
values well above those corresponding to the onset of
gross melt fi-acture. The performance of the additive
was better at higher concentrations. Similar results
were obtained for copolymers of tetratluoroethylne/
perfluoro(propy1 vinyl ether) ('IEFL,C)N@ PFX340/345/
350)(90,91).
As in the case of fluoropolymers, the method of dispersion preparation has a crucial effect on the dispersion quality and, subsequently, the effectiveness of the

wire coating.

JOURNAL OF WNYL & ADLWrrVE TECHNOLOGY,MARCH 2002, Yo/.8, No. 1

17

E. C.Achiueos, G. Georgwu. and S. G. Hatzikiriak0s

, ,,I
PE Exact 3128
T=163 OC Crosshead: D=3.0 mm, d=l.524 mm
8

0.01% BN
0.05% BN

Open symbols correspond

to smooth extrudate

8
1

0.9

0 0
A

0.8 0

8
102

V 8a!@?*

0.5% BN

Ffg. 9. l k e f f i t of BN Conceniration on the processability of PE Exact 3128. (Ent~&tle extruder with

Nokia Maillefer cross-head die,
3.00 rn die, 1.52 mm tip,163OC).

6'1 1
il

103

Apparent shear rate (&), s-'

18

JOURNAL OF VINYL & ADDmVE TECHNOLOGY, MARCH 2602, Vol. 8, No. 1

Role of Processing Aids in Extrusion

Q- 11. Ewtnrdate samples to iUustrate the eff'ectof BN (ClF5)concentration on the extrude appeamnce of m - D P E Exac@31 28
obtained at 617 s-l arld 163C:1) pure resin:2) 0.02% BN: 3)0.1% BN;4)0.5% of BN (ClF5).

processing aid. W n g grounded polymer with a concentrated BN-grounded polymer master batch (i.e.
10% BN) in either a single-screw or twin extruder, and
obtaining the polymer material in a pelletized form resulted in more uniform dispersions and higher effectiveness in instability elimination than dry mixing of
the BN powder with ]polymerpellets. which resulted in
only minor instabilily suppression (31. 92-95). This
effect is similar to tttat obtained in the case of traditional fluoroelastomers. where the dispersion should
be prepared by means of melting a master batch first.
The effectivenessof' BN in eliminating the flow instabilities depends not only on the concentration of the
additive but also on the type of powder used. Several
BN powders were tested for their ef6ciency. The basic
powder was CTF5.which has an average particle size
of 5 bm. CTL40 is an agglomerated version of C F 5 ,
and CTUF contains higher concentration of boron oxide than CTF5. Agglomeration and presence of oxides
are two factors signifitmtly alecting the performance
of BN as a n effective processing aid. Table 2 summarizes the morphological characteristics of the all
powders used in literature and the maximum shear
rates achieved in capillary extrusion experiments of
m - D P E at 163OC, using a cross-head die (31.92-98).
Dispersions of CTFS,CTUF,and CTL40 were prepared
using a single-screw extruder, and dispersions of
BN427-BN431 were prepared with a twin extruder.
The concentration dependence of powder performance
and the optimum concentrations for each powder are
indicated. The best additives, CTF5 and BN431, were
the non-agglomerated powders, in the size range of
5-10 Fm. containing minimum amounts of h03(9297). Properly dispersed in the polymer, at optimum
concentrations, and with the preferable geometry
(cross-head die), these two additives can postpone the
onset of gross melt fracture to high shear rates (9401030 s-9, which are far beyond the value that gross
melt fracture appears in the virgin resin (500 s-l).

The fact that the effectiveness of BN as a processing

aid is much more pronounced in cross-head dies than
in annular ones indicates that the mechanism by
which BN reduces instabilities is geometry-dependent.
The cross-head die, illustrated in Flg. 8, has a gradually convergent entrance. The polymer entering the die
flows through this converging channel in a smooth
fashion. As mentioned in the Introdamtion, experiments have shown that flow irregularities at the die
entrance may be responsible for gross melt fracture.
These flow irregularities. which result in symmetry loss,
are more prone to occu in annular dies than in the
smoothly convergent cross-head die. Yip et at (93)examined whether gradual reduction of the annular die
entrance angle will lead to the results obtained by the
cross-head die. They carried out extrusion experiments
with m-LLDPE in the presence of BN (CFIW) using
capillary dies with angles ranging from 8" to 150". The
reduction of the angle resulted in Merent flow curves,
but it had no effect on the onset of the instability, or
the extrudate appearance. Similar results were found
by Rosenbaum et aL (90).Smaller angles, i.e. < 2",
might have been more effective in mimicking the emshead die effect. However, such angles would result in a
die length comparable to the one of the reservoir (93).
Reducing the entrance angle of annular dies does not
necessarily mimic the flow pattern in the cross-head
die, since the flow in the slowly converging channel of
the latter resembles more the flow between parallel
plates, rather than the flow in a pipe. Even though,
for both types of dies, the onset of sharkskin for the
pure resin occurs at about the same shear rate, it is
possible that BN particles may &ect the flow field, reducing the flow irregularities in a complex manner that
is geometxy-dependent. Further experimental studies,
involving detailed flow visualization. are needed in order
to resolve this issue.
In all the experiments mentioned above, where BN
was used as a processing aid. the flow curves did not

JOURNAL OF VINYL & ADLWIVE TECHNOLOGY, MARCH 2oM, Vol. 8, No. 1

19

E. C. Achilleos, G. Georgiou, and S. G. Hatzikiriak0s

show any significant deviation from that of the virgin

resin, with the exception of BN43 1, which had a slight
shift to lower shear stresses (31). It was therefore concluded that interfacial slip, which typically results in a
shift of the flow curve, cannot account for the instability elimination for the BN powders (which do not shift
the flow curve). However, this might occur only locally
at the exit of the die, which is the location of the origin
of sharkskin.Steady shear experimentswere performed
with a sliding-plate rheometer in order to determine
whether slip is responsible for the effectiveness of
BN431 (31,94).The flow curve of m-LIDPE was gapdependent, shifting to hgher shear rates at higher gap
spacing. Reduction of BN concentration diminished
this effect, as the flow m e of the virgin resin was gapindependent. It was therefore concluded that slip is
indeed the main mechanism by which BN431 aids in
instability elimination. While interfacial slip at the exit
accounts for the elimination of sharkskin, the mechanism for gross melt fracture elimination is different,
and this will be discussed below in a separate section.
In order to investigate the effect of BN surface energy
on the elimination of gross melt fracture, the surface
energy of Merent BN powders was measured with a
modified hi&-pressure capillary rise technique (96.
97).The method allowed for uniform compaction of
powder, and employed a computerized data acquisition
method, which reduced experimental error. The results
are summarized in Table 1 , along with the overall surface energies and the dispersive and nondispersive

components. Powders with small surface energy and

relatively high dispersive components were the most effective processing aids. CTUF, which performed poorly
as a processing additive, had the higher surface energy,
which was justitied by its high content in boron oxide.
This explanation was also supported by the fact that
CTUF performance as processing aid was independent
of powder concentration (31).CTF5 and BN427-430
have comparable surface energies. However, only CTFF,
eliminated gross melt fracture. This is attributed to the
high dispersive energy that cTF5 has in comparison
with BN427-430.It was suggested that high surface
energy has a negative effect on the lubricating action
of the powder because it promotes polymer chain absorption, and that the dispersive component has a
positive effect because it promotes particle migration
to the wall, which facilitated smoother polymer flow.
These findings support the hypothesis of Rosenbaum
et d (90)that even though BN does not promote slip,
it can still act as a lubricant by creating apparent slip
in the layer adjacent to the wall due to generation of
variable viscosity zones.
The effect of BN on the rheological properties of the
process polymers and its relation on instability elimination was examined by Hatzikiriak0s and co-workers
(31,91,94).Linear oscillatory shear experiments (frequency sweeps), carried out in a Rheometrics System
IV parallel-plate rheometer for virgin and BN (CnU)
filled metallocene PE resins, have shown that for BNillled resins the slope of the dynamic modulus changes

Table 1. MorphologicalCharacteristicsof the Various BN Powders Tested, and Additive Performance in Terms of CFtical Shear
Rate for the Onset of Melt Fracture in Capillary Rheometer Extrusion of m-LDPPE Using a Cross-head Die at l63'C.

BN
type

Approximate
Particle size
SEM (pm)

b 0 3

content
Agglomeration

("/I

Pure resin

10

Pure resin
CTF5

10

No

CTUF

Dispersion
concentration
(Yo of BN)

42

0.02
0.1
0.5

926

0.02

155
155
155

42

10

No

2%

0.1
0.5

CTL40

40

Yes (size >40)

926
617

0.02
0.1
0.5

62

93
77

BN427

Yes (size > 180)

0.02
0.1

155
77

BN428

1.5

No

0.02
0.1

308

Yes (size>200)

0.02
0.1

155
155

0.02
0.1

124
155

0.02

865
1080

BN429

BN430

20

No

BN431

No

0.1

20

Maximum shear
rate for smooth
extrudate (s-')

124

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY,MARCH 2lM2,Vol. 8, No. 1

Role of Processing Aids in Exbusion

at small shear rai:es, which is an indication of longer
relaxation times due to the presence of the additive
(91).In addition, the complex viscosity of the BN-fllled
resins was slightly higher than the one of the virgin
resins a t low shear rates. However, a t high shear
rates, the storage and dynamic moduli, as well as the
complex viscosity curve, coincide for all resins. Similar
experiments performed for other types of BN powden
(31,941showed that, with the exception of BN431, all
other powders had a minor effect on these properties,
reducing slightly tkie dynamic and the storage moduli.
This effect was more pronounced for BN431, especially
a s its concentration increased. Based on the sliding
plate rheometer results, the effect that BN431 had on
the rheological p r o p l i e s was attributed to interfacial
slip, rather than to changes of the bulk properties.
Cessation of steady-shear and relaxation experiments
carried out in an Interlaken sliding plate rheometer
have also shown that, at small shear rates, the relaxation times of BN(CFI'5) filled m-LLDPE resins are
longer than the ones of the virgin resin, whereas the
relaxation processes, are identical at high shear rates
(90).
It was, thus, concluded that the small effect of BN
on the rheological properties of m-LIDPE, which is apparent only at low shear rates, cannot be used as the
sole factor for explai~lingthe mechanism by which BN
eliminates the flow instabilities.
4.2 Medudsm of thoas M a t
FractureEliminaticm

Rosenbaum (91) suggested that it is possible that

BN alters the tensile deformation properties of the
polymer and changcs its structure characteristics
under stretching, increasing the critical shear rate at
which instabilities oc~mr,instead of the critical shear
stress. This can explaii the elimination of both sharkskin instability. which may result from polymer rupture caused by the high stresses deweloped at the die
exit (14, 27, 291, and gross melt hcture, which may
result from polymer rupture at the die entry, again
caused by high deformations and stresses. However, if
this were the case, tlie addition of BN should have
changed the moduli of the base polymer. It was also
suggested that BN might cause small cracks in the
bulk of the polymer, anid thus release stress, leading to
uniform exbudate (90.91).Another possibility is that
when BN migrates to the surface of the die, it suppresses cohesive failwe by providing lubrication and,
therefore, elhinates grw melt ii-acture.
m t c h k o v et aL (3.1)investigated the mechanism
of gross melt ii-actureelimination using a flow visualization technique (laser speckle-high-speed photography) with an experimental setup similar to the ones
used by Binnington et IZL (99)and Tremblay (100)for
polymer flow velocimetrf.A quartz capillary rheometer
with a sudden contraction from 20 mm to 1.5 mm
diameter was interrogaied with a focused Neon laser
beam and the fluorescent tracer particles from which
the flow lines could be induced were visualized with
a microscope attached to a photographic camera.

Experiments were performed with virgin and BN-fllled

PP at various shear rates. The flow lines during flow of
the virgin PP were smooth, and large vortices appeared
at the comer of the reservoir at low shear rates. With
increme of flow rate, vortex suppression was observed
Mitially. At even higher shear rates (around 650 s-l)
the flow stopped being continuous at the entrance region. The flow in the entry region appeared to be broken into several layers, and each layer moved with its
own velocity. At regular time intervals. Merent in each
layer, the motion stops for a brief period. The closer
the layer is to the center of the stream, the larger and
more frequent are the jumps and stops inside it. This
produced shamlines that looked distorted, and such
streamlines were associated with the occurrence of
gross melt fracture. Overall, this flow pattern indicated
that a cohesive failure in the bulk of the polymer melt
results into local stick-slip instability between the
multiple polymer surfaces. "%is cohesive failure of the
polymer causes gross melt fracture. Addition of 0.1%
BN to the bulk eliminated these discontinuities, and
resulted into smooth flow lines. Moreover, smooth extrudate were produced at these high shear rate. It was
concluded that BN acts as a lubricant within the bulk
material and prevents local stick-slip when the material fails.
4.5 Boron Nitride fn Combination With Other
Ro--wMd.

Combinations of BN powders with fluoropolymer additives in order to further improve the processability of
the polymers were examined by Hatzikirialros and coworkers (91, 93. 95, 96,98). Experiments in capillary
rheometers with cross-head dies with PE Exact 3128
and PE Exceed 116 demonstrated that the combination of both additives results in greater processability
enhancement (91, 93, 96, 98). In the case of PE Exact
3128, addition of 0.05% TEFLON@ or BN shifts the
critical apparent shear rate for hcture from 50 s-l to
1300 s-l or 1800 s-l, respectively, whereas the combination of TEFLON@and BN shifts the critical shear
r a t e t 0 2 4 0 0 s - ~ , a s c a n b e s e e n i n11
~ . (93,95,96,
98). Similar results where obtained for the extrusion
of PE Exceed 116 (91, 96,98). Addition of 0.1% BN
shifted the uitical apparent shear rate for fi-acturefrom
110 s-l to 900 s-l, whereas combination of 0.1% BN
and 0.05% TEFLON@shifted it to 2000 s-l.When used
as the sole additive, BN had no or minimal effect on the
flow m e whereas combination of BN and TEFLON@
resulted in a significant shift of the flow curve. The
shear rates at which stable flow was achieved with
the combination of the two additives were well above
the point that gross melt fracture occurs.
was previously discussed,T E ~ N acts
@ as a slip
promoter, whereas BN does not. The fact that these two
additives have a different mechanism for suppressing
the instabilities explains why their combination results in further instability elimination, i.e. in steady
flows at higher shear rates, whereas increase of the
concentration of either one of the additives does not.

JOURNAL OF VINYL & ADDITIVE TECHNOLOGY, MARCH 2oM, Vol. 8, No. 1

21

E. C. AchiUeos, G. Georgwu, and S . G. Hatzikiriakos

CONCLUSIONS

Product quality and, in general, processing windows

in extrusion of molten polymers are limited by the
various flow instabilities that are observed at high
production rates. These instabilities are attributed to
the complex rheological and constitutive character of
polymers in general, and have been scrutinized by researchers both experimentally and theoretically. While
there are still unresolved issues in comprehending
these phenomena, the industry demands for process
optimization dictate the employment of processing
aids for product quality improvement and energy requirement reduction.
Fluoropolymers have been traditionally used by the
industry for elimination of the sharkskin and the
stick-slip instabilities. Used as coatings, or more effectively in dispersion with the processing polymer, they
typically increase the slip velocity of the extrudate,
therefore reduce the energy requirements for a particular flow rate. Furthermore, they shift the critical shear
rates for the onset of instabilities up to the point of
the onset of gross melt fracture, therefore permitting
higher production rates. Migration of the fluoroelastomer particles to the wall of the die, with consequent
die coating and lubrication at the polymer wall interface, was determined to be the dominant mechanism
of instability suppression. This was a direct conclusion
of die conditioning measurements, and also proven
with optical microscopy. Fluoropolymer performance
is highly dependent on the dispersion quality; this is
achieved using particles in the size range of 1-5 pm,
thoroughly mixed with the polymer by means of a master batch. Optimization of the additive level (500-1000
ppm), choice of the appropriate additive with the desired interactions with the polymer and/or the wall
and other additives, and use of clean surfaces are also
important.
Stearates, which are typically present in several
commercial polymer resins,are believed to act as PAS
in the case of long-chain branched metallocene polyole&. Processing of these metallocene resins, which
have no other additives, is very similar to the processing of fluoropolymer-containingresins. Die conditioning associated with a steady-state slip enhancement
and instability elimination within a range of shear
rates is observed.
Polymer blending is another traditional method for
improving processing. Similarly to fluoroelastomers,
blending of hydmcarbons, or addition of a hydmcarbon
in a fluoropolymer,can lead to significant reduction of
the power requirement and elimination of the sharkskin and the stick-slip instability. Hydrocarbon blending results in processing behavior and mechanical
properties that are intermediate of the polymers used.
The mechanism by which a hydrocarbon enhances
the processability of fluoropolymers was shown to be
the same as in the case of polymer processing with
fluoropolymers as processing aids.
Use of new processing aids, such as BN and combination~of BN with fluoropolymers.results in immense
22

improvement of the extrusion process. BN powders

used in dispersion with PE resins result in greater increase of the critical shear rate for the onset of instability, especially when a cross-head die is used. In this
case, the instabilities are postponed to shear rates
that are well beyond the gross melt h c t u r e regime.
Conversely to the behavior of fluoropolymers, BN powders do not promote slip, when they are used as the
sole additive. Even though the mechanism by which
BN powders suppress the instabilities is not yet completely understood, it has been experimentally shown
that these additives help eliminate gross melt fracture
by suppressing cohesive failure in the bulk of the
polymer. As in the case of traditional polymers, the
performance of the additive is best when a high quality
dispersion of nonagglomerated particles, in the size
range of 5-10 Fm, at optimum concentration and pmcessing temperature is used. Additionally, it was determined that BN powders with small surface energy and
higher dispersive rather than nondispersive component of free energy are the most effective for suppressing the instabilities.
Finally, the combination of BN with a fluoroelastomer was shown to be the most effective processing
aid. Instabilities are eliminated to even higher shear
rates, and, in addition, the energy requirements are
reduced, as the flow curves are shifted as a result of
slip promotion. Since the two additives have Merent
mechanisms for eliminating the instabilities, their
combination had a synergistic effect.
Comparison of new and traditional processing aids
leads to the conclusion that more than one mechanism is responsible for the onset of instability in each
flow regime. Complete comprehension of these phenomena, as well as of the role of the additives in eliminating the instabilities, is important for process optimization. Elaborate techniques employed recently for
flow characterization in extrusion processes, such as
ATR/FITR (361, fluorescence label chains for velocity
measurements (1011, NMR velocimetry (102), Laser
Doppler velocimetry (103),and detailed flow visualization through quartz/shaphh-e/glass capillary (28, 3 1,
75, 76), can prove valuable in studying the mechanisms of flow instability elimination when processing
aids are present.
A C I L T s
This research was partialty supported by the Cyprus
Foundation for the Promotion of Research (PENEK
Program 02/2000). One of the authors would like to
dedicate this paper to the memory of Dr. Charles W.
Stewart a researcher who made several important contnbutions to the subject of processing aids. Dr. Charles
Stewart provided continuous support to his research
group and was a continuous source of great ideas.

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